Methacrylonitrile purification



Oct. 3l, 1950 l.. J. sPlLLANE METHACRYLONITRILE PURIFICATION K Filed July l2, 1949 BY Q- Hmmm ATTO RNEY.

Patentec ct. 31',

METHACRYLONITRILE PURIFICATION Leo J. Spillane, Rockaway Township, Morris County, N. J., assignor to Allied Chemical & Dye Corporation, vNew York, N. Y., a, corporation of New York Application July 12, 1949, Serial No. 104,231

1 This invention relates to treatment of crude '.methacrylonitrile synthesis mixtures, in particu- "lar, mixtures obtained in the synthesis of meth- ',acrylonitrile from isobutylene-nitrosyl chlorideadduct.` v ,e The methacrylonitrile synthesis mixtures above referred `to contain as impurities chiey methlacrolein, methacrylaldoxime, the hydrochloric .acid salt of tertiary nitrogen base dehydrohalogenating agent, catalytic organic acid such as phthalic acid and water. It is desired to obtain from these mixtures pure, dry methacrylonitrile and to recover the tertiary nitrogen base and catalytic acid for reuse. I

In accordance Vwith my inventionmethacrolein, ldistilled from metha-crylonitrile synthesis mixtures, removes water as an aqueous azeotrope; the distillate is allowed to separate into a methacrolein layer and an aqueous layer; methacrolein from the distillate is returned to serve as additional azeotropic agent for removal oi water from methacrylonitrile synthesis mixture; and dried crude methacrylonitrile is fractionated to separate puried methacrylonitrile. Ready lseparation vof water from methacrylonitrile is e, thereby obtained, notwithstanding the fact that .water and methacrylonitrile themselves form a low-boiling azeotrope. As a 'further feature oi my invention, aqueous residues of reaction and of distillation ofy the above methacrylonitrile synthesis mixtures are treated with a quantity of alkali, such as sodium hydroxide or sodium carbonate, equivalent to ithef'hydrogen?chloride contained inthese residues; the resulting organic layer containing nitrogen ybase and catalytic acid'i's separated; andthe aqueous layer is` treated with a further quantity of alkali and steamdistilled to remove fall' residual organic base. Complete removal of .organic base permits .recovery vof considerable ,additional quantities of organic catalytic acid from the aqueous residues. The aqueous residue Y"is acidified and residual catalytic organic acid which crystallizes is removed.`

A speciiic embodiment of my invention will now be described with reference to the accompanying diagrammatic flow sheet illustrating the same.

Into reactor I containing quinoline-phthalic acid mixture maintained at a temperature of approximately 180 C., isobutylene-nitrosyl chloride adduct is introduced at a rate to maintain the temperature. A crude methacrylonitrile synthesis mixture is thereby produced.

Methacrylonitrile and other relatively volatile 6 Claims. (Cl. M50-465.9)

2 .i constituents of the synthesismixture are vaporized in the reactor and pass through line 2 to condenser 3 and thence through line 4 to settling tank 5. In the settling tank an organic upper layer and an aqueous lower layer arefformed The aqueous layer is drawn 01T through'line 6 'overhead at temperatures of about 60-72 C. and

are condensed in condenser I6 whence'th'e distillate passes via line I'I'l to phase separator' I8. The organic layer in phase separator I8,V which consists principally of methacrolein saturated with water, is returned via line I9 and valve 2l to still I5. The aqueous layer 4from separator' I8 passes via line 22 and valve 23 to still 8. i'

In still I5 crude methacrylonitrile fractions containing methacrolein and constituents-'boiling above methacrylonitrile are taken 01T as side stream at temperatures about 'l2-123 Chand passed via line 24 to still 25. Still 25 separates overhead at about 67-85 C. methacrolein fractions which are condensed in condenser 2B from which a part ofthe condensate is returned to still 25 as reflux via line 21. Fractions of this distillate coming off above about '72 C. contain appreciable amounts of methacrylonitrile. Such fractions are passed from condenser 26 via line 28 and valve 29 to still I 5 and serve to'enrich the distilland in still I5 with methacrolein. Methyvalve 3I.

Methacrylonitrile is withdrawn as residue from still 25 and passed via line 30 to still 32 wherein it is fractionated to separate it from impurities.

'Ihemethacrylonitrile distillate coming 01T about -90" C. is condensed in condenser 33 from which a part returns to still 32 via line 34 as reilux and the remainder is drawn off via line 35 and valve 316 as product. Residues from still 32, principally methacrolein oxime, are drawn 01T from the system via valve 31.

The non-volatile residue from reactor I and the still residues from stills 8 and I5 are passed into neutralizing tank 38 wherein they are contacted with a quantity of caustic soda solution equivalent to the hydrogen chloride combined with the tertiary nitrogen base (quinoline fraction) contained in these residues. The neutralized mixture is passed to settling tank 39, suitably maintained at temperatures somewhat above room temperatures, e. g. 50-80 C. In the settling tank, an organic layer containing most of the organic base in the residues and about 75% of the phthalic acid in the residues separates as an upper layer. This upper layer is returned to the reactor for reuse. Instead of caustic soda, other alkali such as sodium carbonate may be used in the neutralizations. l

'I'he aqueous layer from settling tank 39 is passed to still 4I wherein it is contacted with an additional quantity of 10% caustic soda solution added from storage via line 50, amounting to about of that employed in neutralizing tank 38. The resulting mixture is steam distilled to separate residual quinoline, which is condensed in condenser 42 and passed to separator 43. The organic layer from separator 43 is returned via line 4D to reactor l and the aqueous layer is returned to still 4|.

The residues from still 4l, after all quinoline has been distilled out, pass via line 44 and valve 45 to acidification tank 46 wherein they are acidified to pH of about 2 with sulfuric acid from storage tank 41. The slurry of phthalic acid formed in acidification tank A45.5 is pumped by pump 48 through line 49 to cooling tank 5l wherein further phthalic a-cid crystallizes. The crystallization slurry from :tank 5I is passed via line 52 and valve 53 to the rotary drum filter 54 which separates the mother liquors as waste from the recovered phthalic acid. The recovered phthalic acid :is returned to the reactor for. reuse.

Suitable pumps, drains, valves, surge tanks, controlling instruments, conveyors and the like may be introduced where desired to facilitate operation as above described.

It will be obvious to those skilled in the art that many modifications and changes may be made in the process specifically described above Without departure from the scope of my invention.

I claim:

l. A process for treatment of crude methacrylonitrile synthesis mixtures derived from isobutylene-nitrosyl chloride adduct which comprises separating such mixture into aqueous and methacrylonitrile layers; fractionating out from methacrylonitrile layer a mixture of water and methacrolein by-products present therein; cooling the resulting distillate to form an aqueous layer and a methacrolein layer; returning methacrolein Yfrom said methacrolein layer to organic layer of crude methacrylonitrile synthesis mixture and continuing fractionation of said organic layer to remove further quantities of Awater therefrom; withdrawing crude methacrylonitrile thus freed of water; and further `fractionating dues are Withdrawn.

3. Process as defined in claim 1 wherein methacrolein separated by fractionation from dried crude methacrylonitrile is withdrawn from the system, and intermediate methacroleinmethacrylonitrile fractions distilled from dried crude methacrylonitrile are recycled to crude wet methacrylonitrile fractionation.

4. Process as dened in claim 1 wherein aqueous residues from methacrylonitrile synthesis and from distillations of rude methacrylonitrile are intermixed with an alkali in amount equivalent to the hydrogen chloride content of said residues; the resulting mixture is separated into an organic base layer which is drawn off and an aqueous layer which is made alkaline and steam distilled to separate residual organic base contained therein; aqueous residue of steam distillation is acidied and organic acid is crystallized therefrom; and organic base and acid thus recovered are recycled to methacrylonitrile synthesis.

5. Process as dened in claim 4 wherein liberation of organic base from its hydrochloride is effected with caustic soda solution and separation of organic base layer from aqueous layer is carried out at temperatures of about -80 C. l

6. A process of dehydrating methacrylonitrile containing water and methacrolein, which comprises distilling a mixture of methacrylonitrile, water and methacrolein, thereby obtaining a distillate enriched in water and methacrolein and a residue enriched in methacrylonitrile, separating at least a portion of the methacrolein from the distillate, introducing separated methacrolein into mixture being distilled, and continuing distillation until substantially all the water is removed from the methacrylonitrile.

LEO J. SPIILANE.

REFERENCES CITED The following references are of record in the iile of this patent:

UNITED STATES PATENTS Wooster May 31, 1949 

1. A PROCESS FOR TREATMENT OF CRUDE METHACRYLONITRILE SYNTHESIS MIXTURES DERIVED FROM ISOBUTYLENE-NITROSL CHLORIDE ADDUCT WHICH COMPRISES SEPARATING SUCH MIXTURE INTO AQUEOUS AND METHACRYLONITRILE LAYERS; FRACTIONATING OUT FROM METHACRYLONITRILE LAYER A MIXTURE OF WATER AND METHACROLEIN BY-PRODUCTS PRESENT THEREIN; COOLING THE RESULTING DISTILLATE TO FORM AN AQUEOUS LAYER AND A METHACROLEIN LAYER; RETURNING METHACROLEIN FROM SAID METHACROLEIN LAYER TO ORGANIC LAYER OF CRUDE METHACRYLONITRILE SYTHESIS MIXTURE AND CONTINUING FRACTIONATIONOF SAID ORGANIC LAYER TO REMOVE FURTHER QUANTITITES OF WATER THEREFROM; WITHDRAWING CRUDE METHACRYLONITRILE THUS FREED OF WATER; AND FURTHER FRACTIONATING SAID METHACRYLONITRILE, SEPARATING METHACROLEIN THEREFROM AND OBTAINING SUBSTANTIALLY PURE METHACRYLONITRILE. 